Chemical sensor using chemically induced electron-hole production at a Schottky barrier

ABSTRACT

Electron-hole production at a Schottky barrier has recently been observed experimentally as a result of chemical processes. This conversion of chemical energy to electronic energy may serve as a basic link between chemistry and electronics and offers the potential for generation of unique electronic signatures for chemical reactions and the creation of a new class of solid state chemical sensors. Detection of the following chemical species was established: hydrogen, deuterium, carbon monoxide, molecular oxygen. The detector ( 1   b ) consists of a Schottky diode between an Si layer and an ultrathin metal layer with zero force electrical contacts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of application Ser. No.10/846,433 filed May 14, 2004, now U.S. Pat. No. 7,057,213, which is acontinuation application of application Ser. No. 10/170,000 filed Jul.11, 2002, now U.S. Pat. No. 6,903,433, which is the U.S. national phaseof PCT/US99/29363 filed Jan. 19, 2000.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The field endeavor of the invention relates to sensors for detectingchemicals and in particular to a sensor for detecting and distinguishingatomic hydrogen or atomic deuterium oxygen, carbon monoxide, and nitricoxide.

2. Description of the Prior Art

Electron transport through a metal-semiconductor interface is determinedlargely by the Schottky barrier between them.

The detailed pathways of energy transfer in exothermic and endothermicreactions at a metal surface is incompletely understood and offundamental interest. Bond formation energy of up to several electronvolts is transferred into the substrate during such exothermicreactions. Since bulk phonon energies are typically two orders ofmagnitude smaller, it has been appreciated by the prior art thatnon-adiabatic excitations of electron-hole pairs may be an alternativeto the creation of multiple phonons as a mechanism for sensor detectors.With surface reactions at thermal collision energies, there are fewexamples of energy transferring to the electronic system accompanied bylight emission or chemiluminescence and exoelectron ejection.Chemiluminescence and exoelectron injection are observed only withexothermic adsorption of electronegative molecules on reactive metalsurfaces. In addition, exoelectron emission requires that the metal havea low work function. Heretofore, there has been no direct experimentalevidence for adsorption induced electron-hole pair excitations attransition metal surfaces.

Therefore, what is needed is some type of sensor design or principle inwhich adsorption induced electron hole pair excitations at a transitionmetal surface can be exploited to provide a chemical sensor.

BRIEF SUMMARY OF THE INVENTION

The invention is a silicon device structure, or more specifically ametal-semiconductor Schottky diode, which exploits the current-voltagecharacteristics of the diode for separation of charge and theinteraction of the surface adsorbates on the metal to produce electronsor holes of sufficient energy to transverse the ultrathin metal film andcross the Schottky barrier. The structure allows reliable, zero forceelectrical contacts to be made to metal films less than 100 Angstromsthick. In one embodiment two metalized contacts are deposited usingphotolithographic techniques on a 4000 Angstrom oxide layer prepared onSi (111). The oxide is etched from between the contacts and the exposed6 mm×6 mm Si (111) surface is wet chemically treated. Under vacuumconditions ultrathin metal is deposited onto the device to form a diodeunder well defined conditions.

The sensor device may be microfabricated on n- or p-doped semiconductorwafers. In the illustrated embodiment p_(n)=5-10 Ωcm, p_(p)=1-20 Ωcm, inan ohmic contact is provided on the back of a wafer by means of As⁺ andB⁺ ion implantation, respectively. Isolated from the silicon, the thickgold contact pads are evaporated on a 4000 Angstrom thermal oxide layeron the opposing or front side of the device. A 0.3 cm² window ischemically wet etched through the oxide layer between the isolated goldpads through the use of buffered hydrofluoric then transferred into anultrahigh vacuum chamber (p≈10³¹ ⁸ Pa) for metal deposition andmeasurement.

Copper and silver films, for example, are deposited by e-beamevaporation at substrate temperatures of 135° K. The nominal thicknessis measured by a quartz microbalance. The etching of the oxide producesan angle of inclination between the oxide and the top surface of thesilicon substrate with typically 25°. The evaporated thin metal filmsare connected to the thick gold pads across the small inclination angleto provide a zero force front contact to the device. This contact designallows electrical contact for the current/voltage measurements betweenthe front contacts and back contact even with film thicknesses below 80Angstroms.

In preliminary experiments investigating the energy transfer duringchemisorption, a new process has been discovered associated withchemisorption of atomic hydrogen or atomic deuterium on Ag and Cuultrathin films. When these metals are deposited (30 Angstroms-150Angstroms) onto Si(111) in a Schottky diode detector structure, acurrent is generated associated with an incident atomic H or D beam onthe film. It is hypothesized that this “chemicurrent” is a result ofchemisorption induced excited charge carriers which traverse theSchottky barrier. That energy transfer from chemisorption can proceed bydirect electronic excitation is a significant departure from theconventional dogma which holds that multiple phonon excitation is themeans through which the heat of adsorption is dissipated.

The implications of this observation for the study of surface catalyzedreactions are many. In addition, this process serves as a basic linkbetween chemical processes and electronics and offers the potential forthe generation of unique electronic signatures for chemical reactionsand the creation of a new class of solid-state chemical sensor. Thefirst direct means of measuring atomic H or atomic D separate from thediatomic molecule is demonstrated below. More importantly, it may alsobe possible to differentiate H from D on the basis of the signal. It isexpected that there are unique chemicurrent signals associated with manytypes of surface reactions.

Hot electrons and holes created at a transition metal surface, such as asilver or copper surface by adsorption of thermal hydrogen and deuteriumatoms can be measured directly with ultrathin-metal film Schottky diodedetectors on silicon (111) according to the invention. When the metalsurface is exposed to these atoms, charge carriers at the surface travelballistically toward the interface. The charge carriers are detected asa chemicurrent in the diode. The current decreases with increasingexposure and eventually reaches a constant value at a steady stateresponse. The invention uses the first discovery of a non-adiabaticenergy dissipation during adsorption at a transition metal surface as ameans of providing a chemical sensor or thin film “nose” able to sniffout the presence of chemicals.

The mechanism of the invention is based on the speculation that althoughthe maximum energy of any hot charge carriers are smaller than the metalwork function of the transition metal surface thereby precludingexoelectron emission, the energy of the hot-charged carriers may besufficiently large enough to enable the charge carriers to be collectedby crossing a smaller potential barrier. As will be described below thedirect detection of chemisorption-induced electron-hole pairs isfeasible using a Schottky barrier by transition metal-semiconductordiode detector. The invention shall be described in terms of an atomichydrogen adsorption on copper and silver film surfaces, however, it isto be expressly understood that many other chemical molecules orelements may be detectable on these and other different thin film metalsurfaces according to the teachings of the invention. Silver and copperfilm surfaces exhibit high reactivity to atomic hydrogen, but negligibledisassociative adsorption of molecular hydrogen, H₂. The formationenergy of the hydrogen-metal bond is large, about 2.5 electron volts inboth cases. To detect the hot charged carriers, a sensor is providedwhich is comprised of a large area of metal-semiconductor contact withan ultrathin metal film.

The device structure allows current-voltage curves to be measured fromwhich Schottky barrier heights and ideality factors as a function ofmetal film thickness can be determined. It is observed that barrierheights increase and ideality factors decrease with increasing metalfilm thickness (10 Angstroms to 100 Angstroms). Room temperatureannealing of diodes produced with a low temperature metalizationincreases the measured barrier heights and lowers the ideality factors.The magnitude of these effects depends on the metal used. Results foriron and copper on silicon (111) substrates are among the embodimentsdescribed below.

The rectifying properties of the Schottky diode formed are improved byannealing the devices to room temperature and cooling back to 135° K.The measured I-V curves can then be analyzed using thermionic emissiontheory. Effective barrier heights of 0.6-0.65 electron volts and0.5-0.55 electron volts were determined for copper and silver films of75 Angstrom thickness on n-silicon (111), respectively. On p-silicon(111), silver and copper diodes showed barriers of 0.5-0.6 electronvolts. Ideality factors between 1.05 and 1.5 indicate that large areadiodes are laterally nonuniform and exhibit a barrier heightdistribution.

The invention now having been briefly summarized turn to the followingdrawings wherein like elements are referenced by like numerals.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1( a) is a Fermi diagram of the chemicurrent detection. Hydrogenatoms react with the metal surface creating electron-hole pairs. The hotelectrons travel ballistically through the film into the semiconductorwhere they are detected.

FIG. 1( b) is a schematic side cross-sectional view through a hydrogensensing Schottky diode made according to the invention as described bythe Fermi diagram of FIG. 1( a). The ultrathin metal film is connectedto the gold pad during evaporation.

FIG. 1( c) is a plan elevational view of the device of FIGS. 1( a) and1(b).

FIGS. 2( a) and 2(b) are graphs of the chemicurrent as a function ofhydrogen exposure time for diodes with thin silver and copper films,respectively in a device shown in FIGS. 1( a) and 1(b). The transientscorrespond to the filling of empty adsorption sites by atomic hydrogenon the metal surfaces. The steady-state currents are explained by abalance of abstraction and re-adsorption of atomic hydrogen.

FIG. 3 is a graph of the chemicurrent, I, as a function of time, t,recorded from silver/n-Si (111) diodes of the type shown in FIGS. 1( a)and 1(b) exposed to atomic hydrogen and deuterium. The chemicurrent dueto atomic hydrogen adsorption is multiplied by a factor of 0.3.

FIG. 4 is a graph of the chemisorption current for a 60 Angstrom Ag/Si(111) sensor at 135° K. as a function of the time of exposure to Co.

FIG. 5 is a graph of the chemisorption current for an 80 Angstrom Ag/Si(111) sensor at 135° K. as a function of the time of exposure to CO.

FIG. 6 is a diagrammatic side view of a sensor used for catalyticchemisorption detection.

FIG. 7 is an array of sensors of the type shown in FIG. 10 in which eachone of the sensors has a different catalytic layer so the correspondingsensor detects a different reactant.

FIG. 8 is a graph of the chemisorption current for molecular oxygen on a75 Angstrom Ag/Si (111) sensor at 130° K. as a function of the time ofexposure to O₂.

The invention now having been illustrated in the foregoing drawings, theinvention and its various embodiments now may be understood in contextin the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Electron-hole production at a Schottky barrier has recently beenobserved experimentally as a result of chemical processes. Thisconversion of chemical energy to electronic energy may serve as a basiclink between chemistry and electronics and offers the potential for thegeneration of unique electronic signatures for chemical reactions andthe creation of a new class of solid state chemical sensors. The initialresults have been for an atomic and molecular adsorption, however, it isalso expected that bimolecular surface catalyzed reactions may alsocause direct excitation of charge carriers during the formation of bondsbetween surface adsorbed species. Therefore, in addition to thedemonstrated detection of hydrogen, deuterium and oxygen, sensitivityfor chemisorption for carbon monoxide, carbon dioxide, molecular andatomic oxygen, molecular and atomic nitrogen, nitrogen monoxide andorganic hydrocarbons and other species is expected. Detector responsesto surface catalyzed reactions of several different combinations ofthese species following adsorption are expected to produce achemicurrent including reactions with the combinations of carbonmonoxide and molecular oxygen, carbon monoxide with nitrogen oxide andmolecular hydrogen and oxygen. The basic configuration of the detectorcan be extended to include selective coatings, multi-junction arrays,and tunnel junctions.

The mechanism of current production in a sensor is best illustrated inFIG. 1( a) in the case of hot electrons. FIG. 1( a) is an energy diagramof charge carrier across the metal film to a silicon interface with theposition in the interface being shown on the horizontal axis and energyon the vertical axis. FIG. 1( b) is a corresponding side cross-sectionalview in an enlarged scale of the junction which is grafted in FIG. 1(a). FIG. 1( c) is a plan elevational view of the device of FIGS. 1( a)and 1(b). Transition metallization film layer 10 is evaporated on ann-type silicon substrate 12 forming a diode at their interface 14 with aSchottky barrier Φ illustrated in FIG. 1( a). FIG. 1( a) shows the Fermilevel, E_(F), also denoted by reference numeral 16, the conduction bandminimum, denoted by reference numeral 18 and the valence band minimumdenoted by reference numeral 20. It the exothermic chemisorption ofhydrogen atoms creates electron-hole pairs, hot electrons may travelballistically through metallization film layer 10 and across thepotential barrier of the Schottky diode Φ. The electrodes can bedetected as a current which is defined as the “chemicurrent.” Similarly,hot holes may be measured with a p-type electrode as well as an n-typeas shown in the illustration of FIGS. 1( a) and (b). The charge carrierenergies lie between the barrier height and the adsorption energy, i.e.,between 0.5 and 2.5 electron volts above E_(F) 16. The mean free path(mfp) of electrons and holes in this energy range is typically on theorder of 100 Angstrom, as determined by thermal and field emission,internal photoemission and ballistic electron emission microscopy. Thefilm thickness is in the range of the mean free path of the chargecarriers (electrons or holes).

A silicon based device 22 was developed to facilitate contactingextremely thin metallization film layers 10 during the initial Schottkybarrier formation. Devices 22 were prepared on silicon (111) substrates12 and processed using conventional silicon microfabrication techniquesto produce the device depicted in FIGS. 1( a), 1(b) and 1(c).Microfabricated silicon substrates 12 were made from 3″ diameter 5 Ω-cmphosphorous doped n-type Si (111) wafers. Before processing, the waferswere backside ion implanted with 10¹⁵ cm⁻² arsenic at 150 keV. Afterimplantation the wafers were diced into rectangular samples 0.45-x0.70″.The samples were then cleaned by sonication in water, acetone andisopropanol and were wet oxidized in a tube furnace to grow between 3000and 4000 Angstrom thermal oxide. For the processing of the substrates,AZ5214 image reversal photoresist was used as a positive resist. Twophotolithographic masks were used, one for front metal pads 26 and onefor oxide window 30 between front metal pads 26. The first step of theprocessing was to metalize front metal pads 26. An oxidized siliconsubstrate 12 was spin coated with photoresist and patterned using a UVmask aligner. Metal pads 26 were deposited in a thermal evaporator usingan initial adhesion layer of 100 Angstroms chromium followed by 2000Angstroms of gold. After metalization, the excess metal was removed inan isopropanol sonication lift-off. This completed front metal pads 26and the next step was to make back ohmic contacts 24. The ionimplantation was activated during the thermal oxidation so that underbackside oxide 25 of silicon substrate 12 was n+. Front side 32 ofsilicon substrate 12 was coated with a protective photoresist layer andbackside oxide 25 was removed with buffered hydrofluoric acid, HF. Thebackside metalization was done through an aluminum shadow mask. Backcontacts 24 were Cr (100 Angstroms)/Au (3000 Angstroms) deposited in athermal evaporator. To complete the backside metalization, the frontside photoresist was removed in an isopropanol sonication. The finalstep of the processing was to etch a window 30 in the SiO₂, layer 28between front metal pads 26. The sample was recoated with photoresistand patterned with the mask aligner. The photoresist was developed andthe exposed oxide region was removed with a six minute buffered HF dip.After this step the photoresist was removed by 85° C. H₂O₂: H₂SO₄,solution. The sample was subsequently cleaned and chemically oxidized ina fresh H₂O₂: H₂SO₂solution at 110° C. The final step was to prepare thesilicon surface. After removal from the sulfuric acid, the sample wasdipped in buffered HF for 15 seconds, which was just long enough toensure removal of the chemical oxide off the silicon surface. The samplewas finally rinsed in deionized water and blown dry with nitrogen tocomplete the processing. Because of the etching properties of thebuffered HF solution and the photoresist, the resultant oxide had agentle slope of 15-20 degrees from the unetched SiO₂, down to thesilicon substrate. This angle was independently measured by a scanningelectron microscope (SEM) and an atomic force microscope (AFM). Slopingoxide sidewall 34 allows thin Schottky metallization film layer 10 toconnect continuously from one gold contact pad 26 to the other.

After the final buffered HF dip to prepare a hydrogen terminated andpassivated surface, microfabricated silicon substrate 12 was quicklyindium bonded to a molybdenum sample holder and loaded into an ultrahighvacuum chamber onto a sample manipulator (not shown). The manipulatorhas four independent electrical contacts, two front and two backcontacts. The two front contacts can be actuated from outside the vacuumchamber and were used to electrically contact gold pads 26 on the rightand left sides of silicon substrate 12 while the back contacts 24contact the molybdenum sample holder. After a sample was in place on themanipulator, it was checked for contact-to-contact current leakage. Allsamples used for experiments had room temperature left-front-contact toright-front-contact resistance greater than 100 MΩ and front-to-backresistances greater than 10 MΩ.

Metallization film layers 10 were evaporated by shuttered electron-beamwire evaporators. The evaporation rate depended on the metal used. Inthe embodiment where iron was used, iron was evaporated at 10-watts witha rate of 10 Angstroms min⁻¹, and copper was evaporated with a heatingpower of 16 watts and a rate of 1.5 Angstrom min⁻¹. The evaporatorproduced a collimated flux that deposited a rectangular area of metalonto silicon substrate 12. Evaporated metallization film layer 10spanned metal pads 26 on either side of silicon substrate 12, but didnot extend out to the edge of silicon substrate 12.

Diodes were made on room temperature substrates as well as substratescooled to 130° K. with liquid nitrogen. A Labview virtual instrument(VI) was used to automate current-voltage measurements. The voltagesource was a digital-to-analog board controlled by the computer and thecurrent was measured with a Kiethley picoammeter under GP1B control fromthe computer.

In the present demonstration of device 22, device 22 was maintained at135° K. and exposed to a modulated, thermal hydrogen beam produced by amicrowave plasma. Photons are extracted from the beam to avoidphotoexcitation which can be orders of magnitude stronger than thechemicurrent. A light blocking fixture was developed for the plasma tubewhich prevents photon transmission and thermalized the beam particles asis described in H. Nienhaus, et al., Photon Shield for Atomic HydrogenPlasma Sources” J. Vac. Sci. Tech., A 17 (2), pp. 670-672, 1999. Thecontent of atomic hydrogen, C_(H1), i.e., the number of atoms relativeto the total number of particles in the beam, was measured with aninline mass spectrometer. It varied typically between 7-25% where thevariations were associated with the plasma fluctuations. The kineticenergy of the atomic hydrogen was also measured between 300 and 350° K.The total atomic and molecular hydrogen impinging upon silicon-baseddevice 22 was approximately constant, e.g., about 1013 particles persecond. Hence, with a sensor area of 0.3 cm², the atomic flux variedbetween 3 and 10×10¹² hydrogen atoms per cm²-second. Thereaction-induced chemicurrent was detected between the front metal-pad26 and back contact 24 using standard lock-in techniques. No bias wasapplied to the silicon-based device 22 during measurement. Due to thelow temperature, the noise level was less

Detector current responses as a function of time of device 22 inresponse to atomic hydrogen are shown in FIG. 2 in which thechemicurrent is mapped against exposure times. FIG. 2( a) is a graphshowing the chemicurrent in a silver/n-silicon, interface and asilver/p-silicon interface. FIG.2( b) shows the chemicurrent for acopper/n-silicon diode. The atomic impingement rate, q_(H), was7.5±2.5×10¹¹ atoms per second. At t=0, the beam shutter was opened.Current increases instantaneously upon exposure and decaysexponentially, and eventually reaches a steady state of value as shownin FIGS. 2( a) and 2(b) at each of the diode embodiments. The dipobserved in the 1/t curve for copper at about 2,000 seconds is due to adecrease in atomic hydrogen flux due to plasma instabilities. The atomichydrogen content, C_(H1) decreases from 15% at t=1600 seconds to belowthe detection limit of 2% at t=2,100 seconds in FIG. 2( b) . Thechemicurrent then recovers its original value. The total beam intensity,atomic and molecular hydrogen remained constant during this time. Thus,chemicurrent is only detected if atomic hydrogen is present. FIG. 2( a)shows that chemicurrents were detected for both p- and n-typesilver/silicon diodes, thereby implying that both hot electrons and hotholes are created by the reaction.

The chemicurrent transient shown in FIGS. 2( a) and 2(b) represents theoccupation of empty adsorption sites by atomic hydrogen on metallizationfilm layer 10. The hydrogen coverage, Θ, increases and the adsorptionprobability decreases with the decreasing availability of empty sites.The steady-state chemicurrent observed in the long time limit in FIGS.2( a) and 2(b) is a consequence of a balance between hydrogen removalfrom the surface by abstraction and re-adsorption. The chemicurrent, I,is expected to be proportional to the hydrogen atom flux and thefraction of unoccupied adsorption sites, i.e., I=αq_(H)(Θ_(S1)−Θ), whereΘ_(s) is the saturation coverage if no abstraction occurs and α is aconstant.

If the adsorption of atomic hydrogen and its abstraction by atomichydrogen in the gas phase are governed by the Langmuirian and anEley-Rideal mechanism, respectively, the time rate equation for I and Θobey a first-order kinetics described by:dI/dt∝−dΘ/dt=−(q _(H) /A)[σ_(a)(Θ_(S1)−Θ)−σ_(r)Θ],where A is the active diode area, and σ_(a) and σ_(r) are the crosssections for adsorption and abstraction, respectively. By consideringthe time limits for t=0 and t→infinity, the ratio of the cross sectionsmay be determined from the maximum value, I_(max), and the steady statevalue, I_(S) of the chemicurrent via σ_(a)/σ_(r)=I_(s)(I_(max)−I_(s)).Cross section ratio is calculated from the data in FIGS. 2( a) and 2(b)are 0.2 for the silver/n-silicon diode and 0.4 for the two other diodes.Equation (1) above predicts an exponential decay of the chemicurrentwith a time constant of A/q_(H)(σ_(a),+σ_(f),). Single exponential fitsto the data in FIG. 2 result in decay constants of 480 seconds for thesilver/p-silicon diode, 670 seconds for the copper/n-silicon diode, and750 seconds for silver/n-silicon diode. The observed variation is withinthe range of uncertainties of the beam flux. The cross section ratio anddecay constant allow the calculation of an absolute cross section if theactive diode area, A, and the hydrogen atom rate, q_(H) are known. Withan active area A=to about 0.3 cm², the analysis gives values for σ_(a)of approximately 5×10⁻¹⁶ cm² for silver and 4×10⁻¹⁶ cm² for the copperfilm. With assumed initial adsorption probability of unity, thereciprocal of the cross section σ_(a) is equal to the adsorption sitedensity. From the data, in FIGS. 2( a) and 2(b), the adsorption sitedensities of 2-3×10¹⁵ cm⁻² for both, silver and copper films isobtained. These values are in excellent agreement with the number ofmetal atoms per unit area which is about 2.4×10¹⁵ cm⁻² for silver on(111 silicon) and 3.1×10¹⁵ cm² copper on silicon (111) surfaces. Thisdata supports the interpretation of the l/t curves of FIGS. 2( a) and2(b) given above. Furthermore, the data shows a new way of measuringself-abstraction rates with only one atomic species. In the prior art,the abstraction of atomic hydrogen at surfaces is studied bydeuterium-hydrogen or hydrogen-deuterium exchange reactions.

The chemicurrent is attenuated exponential with increasing metalthickness in the silver/n-silicon diodes. The attenuation lengthcorrelates well with the mfp of electrons in silver, which furthersupports the idea that the charge carriers are created at the metalsurface and travel ballistically through the metal film into siliconsubstrate 12.

The quantitative difference between the n-type silver and copperSchottky diodes shown in FIGS. 2( a) and 2(b) is striking. Thesensitivity may be defined by dividing the initial chemicurrent at t=0by the hydrogen atom impingement rate. This gives the number ofelectrons detected per adsorption event as 4.5×10⁻³ for silver and1.5×10⁻⁴ for copper, an order of magnitude difference. On p-type diodes,the same sensitivity ratio is found. Thus, the difference does notcorrespond to a barrier height difference, which is only observed withn-type Schottky diodes. The sensitivity difference is the standardattributed to two effects. First, the mfp electrons and copper filmshave been measured to be half that of mfp and silver films. Second, theinterface properties of silver/silicon and copper/silicon are verydifferent, e.g., the copper reacts with silicon and may form a silicidewhile similar reactions are not known for silver on silicon. Since thediodes are annealed, copper/silicon interfaces are expected to berougher and have more scattering centers than silver/silicon interfaces.The enhanced roughness may reduce the transmission probabilityconsiderably, in agreement with reported results on mfp in silicidewhich are smaller than in metals.

The p-type silver/silicon diodes seen in FIG. 2( a) are approximately3.5 times less sensitive than an n-type device. These might be explainedby differences in the mfp path of holes and electrons in silver, asobserved previously in gold and in platinum silicon thin films. In theseprior art observations, the attenuation lengths of holes were a factorof approximately 1.5 times smaller than for electrons. Additionally,sensitivity differences may be related to the energy spectra of holesand electrons excited by the surface reactions. The d-bands of bulksilver cannot contribute to the ballistic current, since they are morethan 2.7 electron volts below the Fermi energy. The ballistic chargecarriers thus have nearly a free SP character. The probability ofexciting an electron-hole pair is assumed to depend on the joint densityof states of occupied and empty electronic states. Since the density ofstates of silver increases slightly with energy in the range of ±3electron volts around the Fermi energy, electrons closer to the Fermienergy are excited more effectively. Consequently, the energydistributions of ballistic holes and electrons are not symmetric aroundthe Fermi energy, and on the average the ballistic electrons areexpected to have higher kinetic energies than hot holes. Such anasymmetry would lead to a significant sensitivity difference between p-and n-type diodes.

FIG. 3 is a graph of the chemicurrent as a function of time for atomichydrogen and deuterium reacting with a 75 Angstrom silver film onn-silicon (111). The oscillations in the decay curve for deuterium aredue to plasma fluctuations. Although for the exposure graph of FIG. 3the impingement rate of atomic deuterium was approximately twice aslarge as that for atomic hydrogen, the measured chemicurrent withdeuterium exposure was smaller by a factor of 3, i.e., a sensitivity toatomic deuterium is six times smaller than that to atomic hydrogen. Theslight differences in the strengths of hydrogen and deuterium metalbonds cannot explain this observed isotope effect. A reduced adsorptionprobability for deuterium on silver would also not account for thisobservation, since this would affect the decay rate as well. The decayrates in FIG. 3 differ by a factor of approximately 1.8 which may beexclusively attributed to the flux difference between hydrogen anddeuterium. The isotope effect implies different velocities andinteraction times of the incoming hydrogen and deuterium by a factor ofν². The interaction time, however, is still in the 10⁻¹³ second rangewhich is at least an order of magnitude longer than time constants ofelectron transfer between the substrate and the impinging atoms. For thesame reason, we exclude internal exoelectron emissions which requiresquenching of resonant charge transfer into the affinity level of theapproaching atom accompanied by a drastic change of the surfaceoxidation state.

It is believed that the more relevant mechanism behind the isotopeeffect is likely to be the de-excitation of highly excited vibrationalstates formed under chemisorption. The transition probability betweentwo vibrational levels in a nonharmonic potential decreases the largerthe difference of the two respective quantum numbers. Hence,de-excitation most likely occurs in multiple steps. The spacing betweenthe vibrational levels, i.e., the density of states of vibrationalstates, determines the released energy in each step, and the states inthe enharmonic deuterium-silver potential are closer to each other thanfor the hydrogen-silver bond. Since the formation energies ofdeuterium-silver and hydrogen-silver bonds are almost identical, thedeuterium-silver vibrational energy may be relaxed in more steps ofsmaller energy quanta compared to the hydrogen-silver case. This wouldresult in ballistic charge carriers of lower energies and explain thesmaller sensitivity to deuterium.

In summary, the foregoing disclosure is the first direct detectionreported of hot electrons and holes excited by adsorption of atomichydrogen deuterium on ultrathin silver and copper films as achemicurrent. The current is measured in the large-area unique sensorsthat can discriminate atomic from molecular hydrogen as well asdeuterium from hydrogen atoms. The chemicurrents decay exponentiallywith exposure time and reach a steady-state value. This behaviorcorresponds to occupation of free adsorption sites by hydrogen atoms anda balance between adsorption and abstraction. The currents are smallerif p-type semiconductors are used and if the devices are exposed todeuterium rather than hydrogen. This isotope effect opens a new way ofmonitoring reactions on metal surfaces and will certainly initiatefurther investigations to clarify the mechanism of the excitation. Wehave developed a reliable device structure for the fabrication ofultrathin Schottky diodes.

Many alterations and modifications may be made by those having ordinaryskill in the art without departing from the spirit and scope of theinvention. Therefore, it must be understood that the illustratedembodiment has been set forth only for the purposes of example and thatit should not be taken as limiting the invention which could be morebroadly or narrowly defined later by patent claims.

For example, it is expected that the chemoelectric phenomena associatedwith atomic and molecular interactions at metal surfaces will be foundto show that chemical reactions at metal surfaces can directly transferreaction energy to electrons in the metal. The phenomena can thus beutilized as the basis of a new class of solid state sensors. Theadsorption induced current of different transition metal-semiconductorcombinations will provide a means of systematically varying therelationships between the adsorbate and the metal surface and theelectronic environment in the metal at the metal-semiconductorinterface, and within the semiconductor. New sensor structures will haveimproved device sensitivity and allow discrimination of the electronenergy with operation at room temperature and above. Bimolecular surfacecatalyzed reactions in addition to chemisorption is usable for directexcitation of charge carriers during formation of bonds between surfaceadsorbed species. In addition to the sensor performance and sensitivityfor detection of hydrogen, several important adsorbates are possibleexpressly including CO, CO₂, O₂(0), N₂ (N), NO, C₂H₂, C₂H₄, and C₂H₆.FIG. 4 shows the chemisorption current as a function of time for CO witha 60 Angstrom Ag/n-silicon (111) sensor of the invention at 135° K. FIG.5 shows the chemisorption current as a function of time for CO with an80 Angstrom Ag/n-silicon (111) sensor of the invention at 135° K. FIG. 8shows the response to molecular oxygen. Each adsorbate will have aunique current intensity and rate of signal decay which will allowdifferentiation of adsorbates.

The sensor response to surface catalyzed reactions of severalcombinations of these species following absorption are with the scope ofthe invention expressly including the reactions of CO+O₂, CO+NO, andH₂+O₂. In the sensor 40 of FIG. 6, a catalytic layer 46 is added on topof metal layer 44 disposed on doped silicon layer 42 fabricated in amanner consistent with the teachings of the invention. The chemisorptioncurrent is measured by an integrating voltage amplifier 48. Catalyticlayer 46 is chosen specifically to catalyze a selected reaction whichthen directly interacts with metal layer 44 to create a measurablechemicurrent. As shown diagrammatically in FIG. 7, a plurality ofsensors 40 of the type shown in FIG. 6 can then be combined in an array,each one of which plurality of sensors 40 has a different catalyticlayer 46 to detect a corresponding plurality of different adsorbatesthrough x and y-addressing circuits 50 and current detector 52. In thismanner an electronic nose is realized.

The words used in this specification to describe the invention and itsvarious embodiments are to be understood not only in the sense of theircommonly defined meanings, but to include by special definition in thisspecification structure, material or acts beyond the scope of thecommonly defined meanings. Thus, if an element can be understood in thecontext of this specification as including more than one meaning, thenits use later in a claim must be understood as being generic to allpossible meanings supported by the specification and by the word itself.

The definitions of the words or elements of the following claims are,therefore, defined in this specification to include not only thecombination of elements which are literally set forth, but allequivalent structure, material or acts for performing substantially thesame function in substantially the same way to obtain substantially thesame result. In this sense it is therefore contemplated that anequivalent substitution of two or more elements may be made for any oneof the elements in later defined claims or that a single element may besubstituted for two or more elements in later defined claims.

Insubstantial changes from the claimed subject matter as viewed by aperson with ordinary skill in the art, now known or later devised, areexpressly contemplated as being equivalently within the scope of theinvention.

Therefore, obvious substitutions now or later known to one with ordinaryskill in the art are defined to be within the scope of the definedelements.

The invention is thus to be understood to include what is specificallyillustrated and described above, what is conceptionally equivalent, whatcan be obviously substituted and also what essentially incorporates theessential idea of the invention.

1. An apparatus comprising: a metal-semiconductor Schottky diodecomprising: a silicon substrate; an ultrathin metal film located on aportion of said silicon substrate; said ultrathin metal film and saidsilicon substrate together forming a Schottky barrier having thecurrent-voltage characteristics of a diode thereby enabling detection ofa surface adsorbate on said ultrathin metal film; wherein the presenceof said surface adsorbate creates a measurable current resulting fromproduction of electrons or holes having sufficient energy to transversesaid ultrathin metal film and cross said Schottky barrier; an oxidelayer formed on said silicon substrate and having an inclination formedtherein; and at least one zero force electrical contact including ametalized contact electrically connected to said ultrathin metal film;said metalized contact being deposited on said oxide layer and whereinsaid ultrathin metal includes a portion deposited on top of saidinclination in the oxide layer before being connected to the metalizedcontact.
 2. The apparatus of claim 1 wherein the metalized contact isdeposited using a photolithographic technique in an ultrahigh vacuumchamber (p≈10⁻⁸ Pa).
 3. The apparatus of claim 1 further characterizedby two zero force electrical contacts, wherein said oxide layer isetched from between said two zero force electrical contacts to expose aportion of said silicon substrate, said portion of said siliconsubstrate being wet chemically treated before said ultrathin metal filmis deposited thereon.
 4. The apparatus of claim 3 wherein said ultrathinmetal is deposited by e-beam evaporation under vacuum conditions ontosaid silicon substrate.
 5. The apparatus of claim 1 wherein said siliconsubstrate is microfabricated on a doped semiconductor wafer.
 6. Theapparatus of claim 5 further characterized by a n-doped semiconductorwafer having σ_(n)=5-10 Ωcm, and a p-doped semiconductor wafer havingρ_(p)=1-20 Ωcm, and wherein said silicon substrate is (111) silicon. 7.The apparatus of claim 1 further comprising a back ohmic contact formedby means of As⁺ and B⁺ ion implantation onto an oxide layer positionedon a side of said silicon substrate opposite said zero force electricalcontact.
 8. The apparatus of claim 1 wherein said ultrathin metal filmis comprised of copper deposited at substrate temperatures of about 135°K.
 9. The apparatus of claim 1 wherein said ultrathin metal film iscomprised of silver deposited at substrate temperatures of about 135° K.10. The apparatus of claim 1 wherein said ultrathin metal film iscomprised of iron.